A general method for the construction of sevenmembered rings through Pd-catalyzed C(sp 2 )−H carbonylation at the remote ε-position of γ-arylpropylamine derivatives, including chiral α-amino acids, has been developed using Mo(CO) 6 as the CO source, furnishing richly functionalized benzo[c]azepin-1-one derivatives. The readily removable N-SO 2 Py protecting/directing group provides high levels of chemo-, regio-and diastereoselectivity. Furthermore, this method is amenable to the postsynthetic modification of complex molecules such as small peptides.